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S Through Anionic Ring-Opening Polymerization of Ethylene Oxide and Use of Nonprotected Glycidol As Branching Agent

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S Through Anionic Ring-Opening Polymerization of Ethylene Oxide and Use of Nonprotected Glycidol As Branching Agent 7292 Macromolecules 2009, 42, 7292–7298 DOI: 10.1021/ma901323f Fast Access to Dendrimer-like Poly(ethylene oxide)s through Anionic Ring-Opening Polymerization of Ethylene Oxide and Use of Nonprotected Glycidol as Branching Agent Xiaoshuang Feng,† Daniel Taton,*,† Elliot L. Chaikof,‡ and Yves Gnanou*,† †Universite Bordeaux, Laboratoire de Chimie des Polymeres Organiques, ENSCPB-CNRS 16, Avenue Pey Berland, 33607 Pessac cedex, France, and ‡Laboratory for Biomolecular Materials Research, Department of Surgery, Emory University School of Medicine, Atlanta, Georgia 30322 Received June 19, 2009; Revised Manuscript Received August 28, 2009 ABSTRACT: Dendrimer-like poly(ethylene oxide)s (PEOs) were synthesized through a semicontinuous process based on the anionic ring-opening polymerization (AROP) of ethylene oxide (EO), followed by AROP of a mixture of glycidol (G) and propylene oxide (PO). Glycidol was used as branching agent generating two hydroxyl groups after ring-opening, whereas propylene oxide served to prevent the aggregation of the generated terminal alkoxides. A three-armed PEO star was first prepared through AROP of EO from 1,1,1-tris(hydroxymethyl)ethane as trifunctional precursor using dimethyl sulfoxide (DMSO) as solvent. After completion of EO polymerization and without isolating the PEO star precursor, G and PO (molar ratio 1:3) were added in the same batch to be polymerized either sequentially or randomly. This led to a three-armed PEO star with an average number of terminal hydroxyls per arm which depended on the number of G units inserted at PEO chain ends, as determined by 1H NMR spectroscopy. Growth of the second and the third generation of PEO could be achieved upon reiterating the same steps of AROP of EO and subsequent AROP of G and PO (arborization step) in one pot, affording dendrimer-like PEOs of generation 3 with moderately distributed but expected molar masses. In a variant of this strategy, G was copolymerized in the presence of allyl glycidyl ether during the arborization step in order to introduce allylic double bonds at the branching points of the dendrimer-like PEOs. Introduction functions, but possess true oligomeric/polymeric segments linking Widely acknowledged as the reference biocompatible polymer their branching points. The advantages provided by the dendritic used in the biomedical field, poly(ethylene oxide) (PEO), also structure, in particular its multivalency, can be combined with the referred to as poly(ethylene glycol) (PEG), possesses unique unique features of polymers, in the case of PEO its stealth effect. properties such as chemical stability, solubility in both organic From a synthetic point of view, dendrimer-like PEOs are and aqueous media, nontoxicity, low immunogenicity, and anti- synthesized by repeating two elementary steps that are the anionic genicity.1 PEG has found numerous applications as conjugates to ring-opening polymerization (AROP) of ethylene oxide (EO) from multifunctional precursors, followed by the arborization biologically active molecules/substrates (PEGylation), providing 30,31 the latter with a protection from the immune system and with an (branching reaction) of PEO chain ends. However, this enhanced circulation time and efficacy.1-3 Applications of PEG branching reaction always requires the specific design of branch- ing agents, making the synthesis of dendrimer-like PEOs tedious often use R,ω-heterodifunctional oligomers possessing end func- 21-31 tional groups such as amine, carboxylic, thiol, aldehyde, or as that of regular dendrimers that is achieved stepwise. maleimide to react with a variety of ligands.1,4-6 However, low In this contribution, we explore a shorter divergent synthetic molar mass linear PEG precursors with a limited attachment pathway that would allow a fast access to dendrimer-like PEOs capacity are generally employed. Arranging PEG chains into a by directly using glycidol (G) as a branching agent. Nonprotected branched architecture carrying many reactive sites might offer G leads to polydisperse hyperbranched polyether polyols, re- better performance in biomedical applications than with linear ferred to as hyperbranched polyglycerols (HPG), by ring-opening 2,3,7,8 multibranching polymerization (ROMBP). The seminal work by homologues. Branched PEOs possessing a high number of 32 peripheral reacting sites include star-like,7-15 hyperbranched,16,17 Vandenberg et al. has been further revisited by Mulhaupt, Frey, arborescent,18-20 or dendrimer-like PEOs.21-29 Haag, and others who developed a slow monomer addition In recent years, we have developed synthetic strategies leading to process and the use of partially deprotonated multihydroxy- multihydroxy-ended,22,23 pH-sensitive,24 heterodifunctional bou- containing core precursor, in order to achieve better-defined 25 26 materials in terms of molar masses, degree of branching, and quet-type, and asymmetrical Janus-type dendrimer-like PEOs 33-40 and to their applications in the biomedical field. Generally speak- molar masses distribution. Here we make use of G for the ing, dendrimer-like polymers exhibit structural features similar to arborization of PEO chains without resorting to any protection/ those of regular dendrimers, including the presence of a central deprotection steps. A mixture of propylene oxide (PO) and G is core, a precise number of branching points, and outer terminal indeed directly added at the completion of AROP of EO. The role of PO is to minimize the aggregation of the alkoxides, whereas G generates two hydroxyls through its ring-opening. The number of *Corresponding author. E-mail: [email protected] (D.T.), gnanou@ peripheral hydroxyls and hence the average branching multi- enscpb.fr (Y.G.). plicity are given by the degree of polymerization of the short HPG pubs.acs.org/Macromolecules Published on Web 09/08/2009 r 2009 American Chemical Society Article Macromolecules, Vol. 42, No. 19, 2009 7293 Table 1. Molecular Characteristics of Dendrimer-like PEOs of Second Generation and of Corresponding Precursors Obtained Using Glycidol as Branching Agent a c d f 3 g 3 sample conv (%) N(OH) Mn,theo (Â10 ) Mn,NMR (Â10 ) PDI G1a-[HPGNPPO] 60 5.5 5.96 5.20 1.05 G2a 5.5 11.3 11.5 1.06 G1b-[HPGNPPO] 72 12.9 7.83 6.70 1.08 G2b 12.5 13.7 19.9 1.10 G1c-[HPGNPPO] 74 18.2 9.34 7.97 1.10 G2c 18.4 26.2 30.0 1.11 b e G1d-[HPGNPPO] 80 15.3 (2.8) 7.19 5.60 1.12 G2d 14.7 (2.7)e 20.6 17.1 1.12 a In these notations, the number 1 or 2 represents the generation number, and the letters a to d are meant to distinguish PEO samples of a same series. b Glycidol, propylene oxide, and allyl glycidyl ether were introduced as a mixture in the reaction medium; the other samples G1-[HPGNPPO] (a to c) were prepared through sequential addition technique. c The conversion of glycidol calculated based on the amount of glycidol added. d Number of periphery OH groups generated by arborization of PEO chains and calculated using eq 1. e Average number of allyl glycidyl ether units incorporated. f g Mn calculated based on the amount of the added monomers. Determined using eq 2. Table 2. Molecular Characteristics of Dendrimer-like PEOs of Second and Third Generation Obtained Using Glycidol as Branching Agent a c d f 3 g 3 sample conv (%) N(OH) Mn,theo (Â10 ) Mn,NMR (Â10 ) PDI G2a-[HPGN0PPO] 65 22.0 17.6 14.3 1.24 G3a 24.2 36.3 35.3 1.36 b G2b-[HPGN0PPO] 74 47.3 31.0 26.1 1.38 G3b[N0] 51.1 73.4 77.4 1.30 G2b-[HPGN00PPO] 64 49.5 33.9 24.8 1.27 G3b[N00] 57.0 74.3 77.4 1.18 b G2c-[HPGN0PPO] 71 74.0 49.1 45.5 1.18 G3c 78.0 120 131 1.34 e G2d-[HPGN0PPO] 73 45.6 (7.6) 32.8 20.1 1.28 G3d 47.5 (7.6)e 65.7 56.6 1.31 a See Table 1 for notation. b A mixture of glycidol, propylene oxide, and allyl glycidyl ether was introduced as a mixture in the reaction medium; c samples G2-[HPGN0PPO] (b and c) were prepared by sequential addition of the monomers. Conversion of glycidol based on the amount of glycidol added. d Number of periphery OH groups generated by arborization of PEO chains and calculated using eq 1. e Average number of allyl glycidyl ether f g units incorporated. Mn calculated based on the amount of the added monomers. Determined using eq 2. sequence formed. We thus propose a one-pot two-step synthetic addition of 0.3 mL/h. The mixture was cooled to room tem- strategy to dendrimer-like PEOs of second and third generation, perature after addition, and the active species were deactivated combining AROP of EO from partially deprotonated multi- by adding a few drops of methanol. The crude solution was first hydroxylated precursors and use of G as branching agent, in a precipitated using an excess of diethyl ether to remove DMSO. semicontinuous addition process. In addition, G was copolymer- The viscous polymer obtained was precipitated twice again in ized with allyl glycidyl ether (AGE) so as to introduce allylic cooled diethyl ether from a THF solution. The polymer (4.2 g, double bonds at the branching points of dendrimer-like PEOs. 77%) was collected by filtration and dried at room temperature under vacuum. The data pertaining to the first generation thus synthesized are listed in Table 1. Experimental Section Random Polymerization Procedure. A typical synthetic pro- Materials. Ethylene oxide (EO) (Fluka, 99.8%) was distilled cedure of G1d-[HPGNPPO] is as follows. A two-neck 250 mL over sodium into a buret. Diphenylmethylpotassium (DPMK) flask was charged with lyophilized trihydroxymethylethane was prepared according to known procedures21,22 and titrated precursor (64 mg, 5.3 Â 10-4 mol) and dry DMSO (20 mL).
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